New intermediates and process of making same



Patented Nov. 24, 1931 i r v r I UNITED STTES PATENT enone KALIscHER, orrnAnKroRT-oN-THE-Mlirn, Ann wiinnnn znawncx, 011

rncnnnnnnvi, NEAR ,IRANKFORT-ON-THE-MAIN, enmvrlm z, ssrenons mo ERALANILINE worms, INC., on NEW YORK, n. Y,, A CORPORATION or DELAWARE :h

. NEW IiI'rnnMEnIATEs AND :enocnss on MAKING SAME i i No'Drawing.Original application filed July 8 1926, Serial No."121;283, and, -i11,(3'rern any .Tu1y"20 192 5. *Divided and this application 'filed January31, 1928. 'S'eria1'No.'250,951.

This application is a division of our ap- 1.1-dinaphthyl-8.8dicarboxylicacid 1 is i L plication Serial No. 121,283, filed July 7 8,obtainable for. instance by saponifying its 1926. p a 1 diethylicester,which Kalb (*see Berichte der. We havefound that new and valuable in:deutschen'Chemischen Gessellschaft,vol. 457,.

-5 termediate products are obtainable by treat- 7 page 1724)has-prepared by treating l-chlo f 5o ing a compound of the generalformula: ro-8snaphthoic esters with copper powden V 1 The nuclearsubstitutionproducts oil- LL75 dinaphthyl-8.8-dicarboxy1ic -:acid maywbe obtained either by saponifying thex'corresponding esters,-which'aredescribedin'the German Patent No. 280787, for ,instance by heatingthem with alcoholic hydrochloric acidoralcoholic alkalies, orbyiintroducing, I a 'substituent into the nucleus of 1. 1 dinaphthyl-8.8'-dicarboxylic acid itself. aI-t'jfiields, when brominated inglacialacetic-acid, a V monobromo-product, crystallizing fromtri- V Y ,Ychlorobenzene in'yellow crystals and melt- (wherein the Xs stand forhydrogen atoms, mg above 3000 W when treated 'Wlth lexof which one ormore maybe replaced by a monovalen't 'substituent, the Ys stand fordibromocompound, melting above :800 ,C.

h a h b e la ed'b and soluble in sulfuric acid of per cent i3 2x211 1 fi gifi z f i g 2 strength to an olive solut onwhlle thesolumoderateconditions, until the reaction pronon of the q p u t 15 Orange '25 ductis soluble in glacial acetic acid. Ored- 1 O new Compounds correspond tIn order to {further illustrate our nven- 1 f 11 a1 f m 1 5 tlon thefollowmg examples are given we 'y to the o 037mg gener 1 wlsh 1t howeverto be understood, that our 1nvention is not limited to the/particularexamples given nor to the specific conditions men- 7, tioned. The partsare by weight and all temperatures in centigrades. j

Example 1 a until the starting material is dissolved."

V. (wherein the Xs stand for hydrogen atoms,benzoQbenzanthronevcarboxyliclacid, g ythus of which one'or more may bereplaced by a 'formed, lseparates, p. ,5: monovalent substituent and theYs stand for l The new compound crystalllzes from La, hydrogen atoms,which may be replaced by mixture-of glacialvacetic acid-and-alcoholanhalogens). f

cess ofbrominein the cold anorangecolored 65 10 parts of 1.1--dinaphthyl-8.8'-dicarboxso After diluting the solution with.waterthe 3'5 yellow prisms, melting .at 278?. ,It F is easily qsolublein alkalies with a yellow color and in cold concentrated sulfuricacid with abrownish red color quickly changing to green.

7 V Example 2 V Into a suspension of 10 parts of1.1'-dinaphthy1-8.8.-dicarboxyli-c acid in 48 parts of sulfuric acidof48 per cent strength 230 parts of sulfuric acid of 66 Bewareallowed 1. The benzobenzanthrone-carboxylic acid,-

to run whilestirring at about 60. After 7 7 some timethe mass is worked.up'by intro ducing it in wate y as described in Example thus formed,may be purified by dissolving it in"alkalies, filtering the solution andprecipitating with acids.

Analogous products are obtainable by subecting derivatives andsubstitution products of 1.1-dinaphthyl-8.Sfldicarboxylic acid: to

the same process.

-For instance by starting from amonobromo-l'.1-dinaphthyl-8.8-dicarboxylic acid the correspondingmOnobromobenzobehzanthrone-carboXylic acid is obtained, crystak;';lizing from' trichlorob'enzeneiin yellowish 7 orange needles, meltingat 288 2909. It is soluble. in sulfuri-cjacidof 8O per cent strengthwith ,a-redcolor' quickly changing I to'green. 3 W

- The1dibromo-dinaphthyl-dicarboxylic-acid yields, when treated in ananalogousmanner, a dibromobenzobenzanthrone-carboXylic acid,crystallizing from trichlorobenzene in orange colored crystals, meltingabove300 and difficultly solublein cold sulfuric acid quickly changingto green.

The monochloro dinaphthyldicarboxylicacid forms a -monochlorob'enzobenzanthrone-carboxylic acid, melting at 268-5269 Whencrystallized from:monochlorobenzene, corresponding in its properties tothe mono-" bromocompound.

We'claim: 7 W 1. As new products benzobenzanthronecarboxylic acids,having probably the gener al formula: V a V c "wherein;the Xs stand forhydrogen atoms,

of-whichone or more may be replaced'by a monovalent substituent, the Ysstand for' hydrogen atoms, which may. be replac ed'by halogens, whichare when dry yellowish'to orange powders,insoluble in water, soluble of80 per centstrength' with an olive'color V I H wherein the Xs'stand forhydrogen atoms in alkalies to a yellow to brown solution, in, sulfuricacid of about 80 per cent strength;

to an orange to brown solution quickly changing to green.

'2. As a new product of benzo-benzanthrone-carboxylic acid of theprobable formula which is when dry a yellow powder, crys tallizinginyellow prisms soluble in alkalies toa yellow, in concentrated sulfuricacid to a brownish red solution quickly changing to green. V 4

3. The process whlch comprises treatmga compound of the general formula:1

of which one or more may be replaced by a monovalent substituent and theYs stand by halogen, with zinc chloridelin boiling glacial acetic acid''solution until thefreaction product is soluble in glacial acetic acid.

4. The process which comprises heating about lO-parts of1.1-dinaphthyl-8.8-dicarboxylic acid with about 20 parts ofanhydrous'zinc chloride and about 200 parts of glacial acetic. aciduntil the starting material is dissolved and isolating thebenzobenzanthrone-carboxylic acid thus formed.

In testimony whereof, we afiix our signafor hydrogen'atoms which may bereplaced

